WO2024083434A1 - Procédé d'abaissement de l'indice de fluidité d'une composition polymère recyclée - Google Patents

Procédé d'abaissement de l'indice de fluidité d'une composition polymère recyclée Download PDF

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Publication number
WO2024083434A1
WO2024083434A1 PCT/EP2023/076074 EP2023076074W WO2024083434A1 WO 2024083434 A1 WO2024083434 A1 WO 2024083434A1 EP 2023076074 W EP2023076074 W EP 2023076074W WO 2024083434 A1 WO2024083434 A1 WO 2024083434A1
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WO
WIPO (PCT)
Prior art keywords
ethylene
polymer
alfa
composition
recycled
Prior art date
Application number
PCT/EP2023/076074
Other languages
English (en)
Inventor
Mara Destro
Riccardo FIORAVANTI
Original Assignee
Basell Poliolefine Italia S.R.L.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basell Poliolefine Italia S.R.L. filed Critical Basell Poliolefine Italia S.R.L.
Publication of WO2024083434A1 publication Critical patent/WO2024083434A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/20—Recycled plastic

Definitions

  • the present disclosure relates to a process for lowering the melt flow rate of a polymer composition containing at least 50 wt% of a recycled polypropylene composition and at least 5 wt% of polar polymers such as EVOH.
  • an object of the present disclosure is a process for lowering the melt flow rate of a recycled polymer composition comprising at least 50 wt% of a recycled polypropylene composition, and at least 5 wt% of a polar polymer, said process comprising: a) providing recycled polymer composition comprising at least 50 wt% of a recycled polypropylene composition, and at least 5 wt% of a polar polymer; b) adding to the composition from 4.0 wt% to 9.0 wt% based on the weight of the total composition of ethylene-alfa-olefm copolymer or ethylene-alfa-olefin terpolymer wherein one or more alpha olefins are selected from the group consisting of alpha olefins having from 3 to 12 carbon atoms, such as propylene, 1.
  • the ethylene-alfa-olefm copolymer or ethylene-alfa-olefm terpolymer can contains unconjugated diene; furthermore the ethylene-alfa-olefm copolymer or ethylene-alfa-olefm terpolymer has constituents in the form of a maleic anhydride graft (g-MAH); c) melting the composition comprising component a) and b) and d) recover the final polymer.
  • g-MAH maleic anhydride graft
  • the recycled polymer composition comprises at least 60 wt% of recycled polypropylene composition, based on the total weight of the recycled polymer composition, preferred range is from 60wt% to 76 wt%.
  • the recycled polymer composition comprises at least 7 wt% preferably at least 10 wt%, more preferably at least 15 wt% of the polar polymer. Preferred range is from 5 wt% to 25 wt%.
  • a polar polymer is defined as a polymer containing polar groups such as alcohol (-OH), ether (-O-), carboxylic acid (-COOH), amine (-NH2), nitrile (-CN), thiol (-SH) groups.
  • Examples of polar polymer can be polyamide, polycarbonate, poly(, ethyl methacrylate), Acrylonitrile, butadiene, styrene terpolymer, ethylene vinyl alcohol polymer (EVOH).
  • the polar polymer is EVOH.
  • the ethylene-alfa-olefm copolymer or ethylene-alfa-olefm terpolymer optionally containing unconjugated diene are preferably added in a range from 6.0 wt% to 8.5 wt%.
  • the ethylene-alfa-olefm copolymer or ethylene-alfa-olefm terpolymer optionally containing unconjugated diene are for example ethylene proplylene copolymer, ethylene 1 -butene copolymer, ethylene 1 -hexene copolymer and ethylene 1 -octene copolymer, these copolymers being grafted with maleic anhydride (g-MAH). Particularly preferred are maleic-anhydride- modified ethylene-propylene copolymer.
  • ethylene-alfa-olefin copolymer or ethylene-alfa- olefm terpolymer grafted with maleic anhydride which can be used as component (c) are:
  • TAFMER MC201 g-MAH (”0.6%) blend of 67% EP copolymer (20 mol % propylene)+33% EB copolymer (15 mol % 1 -butene): Mitsui Chemicals, Japan.
  • TAFMER MH7020 g-MAH (-0.7%) EP copolymer, Mitsui.
  • EXXELOR VAI 801 g-MAH (”0.7%) EP copolymer; ExxonMobil Chemical, US.
  • EXXELOR VAI 803 g-MAH (0.5-0.9%) EP copolymer, amorph., Exxon.
  • EXXELOR MDEX 94-1 1 g-MAH (0.7%) EPDM, Exxon.
  • FUSABOND MN493D g-MAH (-0.5%) ethylene-octene copolymer, DuPont, US.
  • the Melt Flow Rate of the recycled polypropylene composition, starting material of the process ranges from 10 g/10 min to 150 g/10 min; preferably from 20 g/10 min to 100 g/10 min, more preferably from 25 g/10 min to 80 g/10 min.
  • the recycled polypropylene composition is a Post-Industrial Resin (PIR), the waste generated from the manufacturing process that is reclaimed or used again in the same material or Post-Consumer Resin (PCR), defined as a resin used by the consumer for its intended purpose, that has reached its end of use, and then tossed into a recycling bin is excluded.
  • PIR Post-Industrial Resin
  • PCR Post-Consumer Resin
  • the recycled polypropylene composition contains preferably at least 50 wt%; more preferably at least 60 wt% ; even more preferably at least 65 wt% of derived units of propylene.
  • the remaining comonomers can be ethylene; 1 -butene; 1 -hexene or 1 -octene derived units; ethylene being preferred.
  • Examples of propylene based polymer can be propylene homopolymer, propylene, ethylene heterophasic polymer, propylene ethylene 1 -butene, propylene ethylene 1 -hexene terpolymers and mixtures thereof.
  • the recycled polypropylene composition can be contaminated with other polymers such as polyamide, polycarbonate, poly(, ethyl methacrylate), Acrylonitrile, butadiene, styrene termpolymer, ethylene vynyl alcohol polymer (EVOH).
  • polyamide polycarbonate
  • Acrylonitrile butadiene
  • styrene termpolymer ethylene vynyl alcohol polymer (EVOH).
  • the final polymer obtainable with the process of the present disclosure is a recycled polypropylene composition having an high MFRDetermined according to the method ISO 1133 (230° C, 2.16 kg).
  • the MFR Determined according to the method ISO 1133 (230° C, 2.16 kg) of the recycled polypropylene composition obtainable with the process of the present disclosure depends from the starting MFRinit.
  • the MFR that can be obtained ranges from MFRinit /1.2 to MFRinit /5.0; preferably ranges from MFRinit/1.9 to MFRinit/4.0. More preferably the MFR ranges from 1.3 g/10 min to 8.0 g/lOmin; even more preferably ranges from 1.5 g/10 min to 5.8 g/10min;.
  • the final polymer obtainable with the process of the present disclosure that is a recycled polypropylene composition can be used for examples for obtaining films, in particular cast, BOPP and Blow films.
  • Xylene Solubles at 25°C have been determined according to ISO 16152: 2005; with solution volume of 250 ml, precipitation at 25°C for 20 minutes, 10 of which with the solution in agitation (magnetic stirrer), and drying at 70°C.
  • the sample is dissolved by tetrahydronaphthalene at 135 °C and then it is poured into the capillary viscometer.
  • the viscometer tube (Ubbelohde type) is surrounded by a cylindrical glass jacket; this setup allows temperature control with a circulating thermostated liquid.
  • the downward passage of the meniscus is timed by a photoelectric device.
  • the passage of the meniscus in front of the upper lamp starts the counter which has a quartz crystal oscillator.
  • the meniscus stops the counter as it passes the lower lamp and the efflux time is registered: this is converted into a value of intrinsic viscosity through Haze (on 1 mm plaque)
  • 5x5 cm specimens are cut molded plaques of 1 mm thick and the haze value is measured using a Gardner photometric unit connected to a Hazemeter type UX-10 or an equivalent instrument having G.E. 1209 light source with filter "C". Reference samples of known haze are used for calibrating the instrument.
  • the plaques to be tested are produced according to the following method.
  • rlr2 The product of reactivity ratio rlr2 was calculated according to Carman (C.J. Carman, R.A. Harrington and C.E. Wilkes, Macromolecules, 1977; 10, 536) as:
  • the tacticity of Propylene sequences was calculated as mm content from the ratio of the PPP mmTpp (28.90-29.65 ppm) and the whole Tpp (29.80-28.37 ppm).
  • Films with a thickness of 50 micron are prepared by extruding each composition in a a single screw Collin extruder (length/diameter ratio of screw 1 :25) at a film drawing speed of 7 m/min and a melt temperature do 210-250 °C.
  • the determination of the number of gels per m 2 is carried out by visually detecting the number of gels of a sample film projected by a projector on a white wall-chart with a magnificated scale. Film pieces of 130 x 7.5 cm are cut from a cast film at least 30 minutes after extrusion (die temperature in the range from 250° to 290°C, chill rolls temperature 20°C). The cast film is prepared as above described.
  • the random copolymer has been blended with EVOH , TAFMERMH7020: g-MAH (-0.7%), en ethylene propylene copolymer sold by Mitsui; and RETAIN3000 a copolymer of ethylene/ octene copolymer grafted with maleic anhydride groups, from the Dow Chemical Company.
  • the compositons are reported on table 2

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un procédé pour abaisser l'indice de fluidité d'une composition polymère recyclée comprenant au moins 50 % en poids d'une composition de polypropylène recyclé et comprenant au moins 5 % en poids d'un polymère polaire comprenant les étapes consistant à : a) fournir une composition polymère recyclée ; b) ajouter à la composition de 4 % en poids à 9 % en poids sur la base du poids de la composition totale un copolymère d'éthylène-alpha-oléfine ou un terpolymère d'éthylène-alpha-oléfine greffé avec de l'anhydride maléique ; c) faire fondre la composition comprenant le composant a) et b) ; et d) récupérer le polymère final.
PCT/EP2023/076074 2022-10-18 2023-09-21 Procédé d'abaissement de l'indice de fluidité d'une composition polymère recyclée WO2024083434A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP22202292 2022-10-18
EP22202292.3 2022-10-18

Publications (1)

Publication Number Publication Date
WO2024083434A1 true WO2024083434A1 (fr) 2024-04-25

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108395620A (zh) * 2018-03-28 2018-08-14 中华全国供销合作总社天津再生资源研究所 一种高强度高韧性聚丙烯再生颗粒及其制备方法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108395620A (zh) * 2018-03-28 2018-08-14 中华全国供销合作总社天津再生资源研究所 一种高强度高韧性聚丙烯再生颗粒及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
C. J. CARMANR. A. HARRINGTONC. E. WILKES: "Monomer Sequence Distribution in Ethylene-Propylene Rubber Measured by C NMR. 3. Use of Reaction Probability Mode", MACROMOLECULES, vol. 10, 1977, pages 536

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